Contact insecticide from petroleum



Patented Dec. 10, 1940 i 224,723

UNI-TED s'r-A'rss PATENT OFFICE coNrAc'r INSEC'HOIDE mom rnrnonnm i Carleton niiisluonttiois, N. 1., assignor to Standard Oil Development Company, a corporation of Delaware No Drawing. Application December 24. 1937,

' Serial No. 181,605

This invention relates to the production of in- Aphides or plant lice, as they are commonly secticidal materials from petroleum hydrocarbons. wn. m y be ei her black (C y anthemum) 01 It is particularly applicable to the production of green in color. Although very small in size, they nitrated hydrocarbons and nitro-hydrazones. It Often (10.35 h damage vegetation as do comprises further the production and use of inlarger insects- Under n a W Weather 5 secticidal substances which are'relatively harmmuons they increase astoundmlly fast 8' 8111816 less to ioliase of plants. g g g use g g n g thou Furthermore, this invention proposeslthe use, San ese cc 3 n e on same as starting materials, of hydrocarbon fractions with their beaks buried mm h Plants 5 I readily available from petroleum; ing out the juices flowing to those portions; This The resent invention cum use tn mtmtm'n constant irritation causes deformation or death of oleii i iicgsaturated allphati t i, nzphti lenlc, and or the plant Apmdesmcrete mney'nke mate rial which may finally cover the entire plant as a aryl or aralkyl hydrocarbons, and the like. For i this purpose any [table mtmtmg agent (8. g. sticky, sweetist layer, thereby preventing respira tion of the plant and attracting other insects.

15 nitric acid, mixed nitric-sulphuric acids, oxides ceimm fungi (Capnwummmfly) nve exclusive; 15 nitrogen: etc) may be employed- In this ly on this waste and thereby likewise infest the her, mtl'ated hydrocarbons are obtained said plant, covering it with a smut disease known as nitrated hydrocarbons being valuable as contact p m The red spider (Tetmnychu, mm.

insecticides for use against various in'sectpests. as), and, polyphagous fl f th d, 20 i v on the proposes the. condensation attacks many diverse plants, the leaves becoming of said nitrated hydrocarbons diazonium prematurely djgcqlgred and dropping,- compounds whereby-nitro-hydi;azones of inse'cti- Insect pests of this type are generally comlcldal Value are Obtainedm whlch cali bated by means of contact insecticides, which be converted (e. g. .by means of mineral acidmaterials, on coming in contact with insects, are 25 metallic nitrite, nitrogen trioxide, amyl nitrite, absorbed through the latters shells, thereby causand" the like) into a diazonium compound may ing paralysis of the nervous system or producing be used for the purpose. death in some other manner. One of the most v As is well knownpmany forms of vegetation, Widely used materials of this 018-88 18 nicotine. an

such as vegetables, fruits andflowers, are at- "alkaloid obtained from tobacco. This plant serves 30 '50 tation.

tacked'and infested by various p i of t as the only source of nicotine, which it furnishes Some or the more common of these are the vari- 1 by extraction o ste m l io S e i ous beetles (Japanese, Mexican Bean, etc), the tine is found in tobacco in a very low. concentracodllng moth, the boil weevil. aphides. and red tmn its Yemvery' entails answerable spiders. The first-mentioned of these, the beetle! expense type of insects, because of their hard and im erthis it has been found that vious shells, are usually eradicated by mean: of powerful insecticides can be 5117 Produced m stomach poisons, the type leamusemte etc by-product or low-grade petroleum hydrocarbon and materials being pom to fractions. The treatment involved comprises nitrailing said hydrocarbon mixtures with suitable' and toxic to i'ollageas well. the other hand, mmtmg t, d separating nitration prodhas been d by ucts thus rot-med; r have'found further that these the presentinvention are eiiectivein irllling the mm hydrourbons maybe condensed with soft-shelltype oi insect pest, for example, aphides m compound, to produce ma ma o and red 59 1 1. by contact with-these said nitro-hydraz'ones being efl'ective as contact 45 sects. it has been found further that i acinsecticides. I have found also that nitrated hycomv ish d wi ou im o ting-delete 1 ect drocarbons oinitro-hydra'zones prepared in this to the foliage ofplants andjwithout. endangering way may be eflectively applied, as'insecticides, the health of persons emplo ed ln snmying .vegeeither in the form of emulsions- (e. g. in soap media) or dissolved in lllht hydrocarbonsolvents' (e. g. petroleum ether, kerosene, and the like), or mixed with suspensions of colloidal clays. I

By soap media I means water-soluble detergents and wetting agents comprising not only solutions of salts of fatty acids, but also salts of alkyl sulphuric acids (e. g. palmityl hydrogen sulphate), as well as salts of alkyl and aryl sulphonates, amine salts and the like.

By colloidal clays I include bentonite, fuller's earth, diatomaceous earth, or other material capable of dispersing the insecticidal materials.

By hydrocarbon solvents are included volatile petroleum fractions which evaporate readily, leaving the insecticidal material on the insect as residue.

In some cases the hydrocarbon starting material may be olefinic in nature. An example of this is the product, consisting essentially of octenes, which is obtained by the polymerization of isobutylene, or of isobutylene with normal butylene. This polymerization may be eflected at elevated temperatures with the aid oi! activated clay, alumina, kieselguhr, and the like, or at lower temperatures using such catalysts as sulphuric or phosphoric acids, or aluminum chloride or boron trifluoride, etc. The polymerized oleflns are of true olefinic nature, just as are the unpolymerized olefins, since both fractions contain unsaturated linkages (double-bonded carbon atoms which are lacking in hydrogen atoms and which may form derivatives by addition as well as by substitution). In such cases, the nitration treatment may result in the attachment oi nitrated groups both at the point of unsaturation (by addition) and also at points of saturation (by substitution).

In other cases, as when working with Pennsylvania oils, the amount of unsaturated material present is usually quite low, the hydrocarbon mixture consisting mainly oi parafllnic hydrocarbons. In still other cases, both saturated and unsaturated hydrocarbons may be present in substantial amounts. A typical example of this is Colombian Diesel oil.

It is to be understood-then that by the present invention, the nitrated products may contain nitrated groups such as nitrites (----ON()) and nitrates (-ONOz) in which carbon and nitrogen are separated by oxygen. In addition, nitrated groups such as the nitroso (-NO) and nitro (NO:) groups, in which carbon is attached directly to nitrogen, may also be present.

In many cases or nitration it is sometimes difllcult to entirely eliminate oxidation. It the latter phenomenon occurs, then traces of nitrogen tetroxide (N204) or nitrogen trioxide (N203) may result. These oxides of nitrogen may then react with previously formed nitro compounds to give nitrolic acids (with primary nitro group to ive N'O CHN| and pseudonitroles (with secondary nitro groups to give /NO|) -c-na These latter materials may, if desired, removed (by weak alkaline extraction, etc.), or they may,

be retained in the nitrated product for their insecticidal-Name.

By the term nitrated product," then, is meant all productsresulting by the action 01' nitric acid,

or other suitable nitrating agent, on a petroleum hydrocarbon starting material, said petroleum hydrocarbon starting material containing any, several, or all of: olefinic, saturated aliphatic, naphthenic, aryl or aralkyl hydrocarbons.

As hereinbetore mentioned, the nitrated products may contain nitro groups acidic in character; for example, as when the starting hydrocarbon mixture is olefinic in nature, or as well when the starting material contains olefinic material along with saturated aliphatic, naphthenic, and aromatic hydrocarbons, or even when the olefinic and aromatic contents of the starting material are low and the paraiiinic and naphthenic contents are high. When these acidic nitro groups are present, the tendency toward alkali solubility is imparted to the nitrated product, the extent of which tendency is governed by the weight 0! the nitrated molecule, the number of acidic nitro groups, and the influence of other groups. Said acidic nitro groups are advantageous for the preparation of insecticidal sprays insofar that said nitrated products tend to be more soluble in aqueous or weak alkaline solutions, have better wetting afllnity for insect pests. are more compatible with aqueous soap solutions (e. g. 1:1000 potassium oleate solution, and the like), and are rendered less volatile and hence remain effective for longer periods. In some cases, however, it may be desirable to apply the insecticidal material in organic solution. This is easily accomplished by dissolving the nitrated product in any common organic solvent (e. g. alcohol, acetone, gasoline, kerosene, benzene, etc.) the presence of the groups of nitration often making the nitrated product more easily miscible with organic liquids. In some cases, however, it desirable, the nitrated produc may be further condensed with appropriate diazonium compounds to produce nitrated hydrazones, which materials likewise possess strong insecticidal properties. This condensation may be accomplished by reacting the nitrated products, in the presence of alkaline materials (e. g. sodium hydroxide, potassium carbonate, and the like), with diazonium compounds. These diazonium compounds may be prepared (by treating organic amines with a mineral or other acid and a metallic nitrite, etc.)

to produce simple or substituted nitro-hydrazones. By organic amine I mean any amine compound, naphthenic, aromatic or heterocyclic, which can be converted, by diazotization or other means, into a diazonium compound. Nitro-hydrazones thus formed may be used in any of several forms, as described hereinbeiore, as insecticidal sprays and the like. This-condensation may be illustrated by the following example:

icfls (-SO3H. -COOH, etc.) which would tend further to make the final product more easily soluble in dilute alkali or soap solutions.

The nitrated hydrazones possess a further advantage, as outlined by this invention, in that the former are true dyes, the nitro groups serving' as chromophores, while the grouping present in nitro-hydrazones serves as auxochromei' As is. well known, dyes possess marked specificity and enhanced activity in regard to absorptive tendencies toward textile fibers and certain organisms and the like, and, therefore, the nitro-hydrazones would thus be, expected to exert a similar effect toward insect organisms.

The first step in the treatment represented by this invention comprises mixing hydrocarbon starting materials with a nitrating agent (e. g. mitric acid of the appropriate strength) and emciently agitating, with or without heat, as found ations made batch or continuous. 'The nitrated product may be separated and refined (e. g. by washing thoroughly with water and drying or by neutralizing mineral acid with limestone, etc.). If desired, the nitrated'portion may be separated from any unnitrated material (e. g. by distillation under vacuum or with the aid of steam, or-

by solvent extraction, for example, with aniline or alcoholic alkali, etc.) If desired the nitrated portions may be converted into nitrated hydrazones by treatment with alkali (e. g. sodium hydroxide in aqueous-alcoholic solution) and slowly adding this. solution, while kept cool, to an aqueous or aqueous-alcoholic solution'of a diazonium compound. The latter may be prepared by the methods hereinbefore mentioned and the parent substance may be an-aromatic, or substituted aromatic amine (e. g. aniline, nitro-aniline, sulphanllic acid, and the like). The nitrated hydrazones thus formed may be recovered and refined by dilution with water, accompanied by possible acidification with dilute acid (depending upon the specific nature of nitrated hydrazone), followed by washing with water and drying.

I have found that the nltro-hydrazones described'herein possessed the tendency to dissolve in aqueous mineral acids as well as in alkaiies.

This comes by virtue of thesecondary amino grouping possessed 'by these nitro-hydrazones. I: desired,

the nitro-hydrazones may be dissolved in mineral acids (e. g. strong hydrochloric acid) and greatlydiluted with water, whereupon stable colloidal -the:bercin'beifor'r-described-Q-insecticidal materials suspensions of the-nitro-hydra'zonesor their-salts result. y Y

For application to insect-infested vegetation.

may-b dissolved lnj'ga volatile organic solvent,-

- sprayed onto the insects', and the solvent allowed to evaporate. Or, if it isdesirous to use spray preparations, the nitrated hydrocarbons or nitrated hyd'razones may be added, as such, or thinned with a small amount of a solvent, to dilute soap solutions while the latter are being vigorously agitated by means of an efficient stirrer. If desired, this may be accomplished by the aid of heat. In some cases, in which the nitrated hydrocarbons or nitrated hydrazones con.- tain acidic nitro groups. it may be necessary to add small amounts of alkali to their soap emulsions to render them more stable. alkali is added in amounts just sufiiclent to produce slight pink colors when tested with phenol-. phthalein.

My invention is illustrated by the ollowing typical examples:

In such a case Example 1.--To 250 partsiiy volume of an olefinic material (a water-white mobile liquidof specific gravity 0.730, prepared by the co-polymerigation of normal butylene and isobutylene and consisting principally of o'ctenes) were added 125 parts by volume of nitric acid or specific gravity 1.20 (30-33 per cent HNQa). The mixture was agitated and heated under reflux at 70 C. for 2 hours. aqueous layer (spent acid) was withdrawn and i replaced by a similarvolunie of fresh nitric acid of 1.20 specific gravity and the nitration treatment repeated. After five such treatments the specific gravity of the nitrated product (a yellow oil) had reached 1.115. This oil, after washing and drying over anhydrous sodium sulphate, was obtained in a yield of 210 parts by volume.

Example 2.-'A solution (A) was prepared by dissolving 10 parts by weight of the nitrated co- At the end of this time the dimer, as prepared in Example 1, 5 parts-by weight of potassium hydroxide; and parts by weight of water in parts by weight of ethyl alcohol. A'second solution (B) was prepared by adding slowly 4 parts by weight of sodium nitrite to a cold solution of 5 parts by weight of aniline and 17 parts by weight of 93 per cent sulphuric acid in 250 parts by weight of water, this being followed by the addition of 22.5 parts by weight of sodium acetate. While still cold (0 to +5 0.), solution (A) was added slowly. and with stirring, to solution (B).

A deep red oil -immediately separated. After standing for 50,

several hours the nitro-hydrazone material was recovered by extraction with ether. This solution was dried over anhydrous sodium sulphate,

and the ether-evaporated. The residue. a deep red oil, dissolved in alcohol, ether, acetone, benzene, gasoline, and-heavy mineral oil. It was also found to be soluble in strong mineral acids, e. g.

.concentrated hydrochloric acid. On dilution of the hydrochloric acid 1 solution of this nitrohydraaone material, a stable colloidal suspension was obtained.

Example 3.-A sample of Pennsylvania Diesel oil, an almost colorless liquid of specific gravity 0.825 (consisting essentially of paraflnlc hydrocarbons, with smalier proportions of olefinic and aromatic hydrocarbons, bromine number 0.0446;

0.0448.mg. b romine per mg. Pennsylvania oil), was nitrated in the following manner; One hun: dred parts by volume of Pennsylvania oil and 20 parts by volume ofnitric acidofspecific grave ity 1.4216849 vper cent HNOs), were agitated at 25? 051,01 llihours. ,Atfthe end of this time the oily layerwas separated'from the spent acidand a small amountiabout l-T'per cent) of sludge, washed thoroughly with water over calcium chloride. The product, a yellow oil, possessed a specific gravity of 0.839.

Example 4.A solution (A) was prepared by adding 41.9 parts by weight of the nitrated Pennsylvania oil from Example 3, 5 parts by weight of potassium hydroxide, and 50 parts by weight of water to 200 parts by weight of isopropyl alcohol. A second solution (B) was prepared by dissolving the following materials in 250 parts by weight of cold water in the order given: 17 parts by weight of 93 per cent sulphuric acid, 5 parts by weight of aniline, 4 parts by weight of sodium nitrite, and 22.5 parts by weight of sodium acetate. While both solutions were cold to C.) (A) was added slowly to (B). The red, oily nitro-hydrazone material separated and was recovered by extracting with ether and evaporating the latter.

Example 5.-A sample of Colombian Diesel 011 of specific gravity 0.847, and which contained considerable unsaturated material (bromine number 0.276; 0.276 mg. bromine per mg. Colombian oil) along with aromatic and saturated aliphatic hydrocarbons, was nitrated in the following manner: One hundred parts by weight of this Colombian oil and 25 parts by weight of nitric acid of specific gravity 1.09 (15 per cent HNOa) were agitated at 70 C. for 12 hours. The resultin oily layer was separated from the spent acid and a small amount (about 1 per cent) of sludge and washed thoroughly with water and dried. The dark-colored oily product possessed a specific gravity of 0.880.

Example 6.A mixture (A) was prepared of the following constituents: Twenty-two parts by weight of the nitrated Colombian oil from Example 5, 2.5 parts by weight of potassium hydroxide, 25 parts by weight of water, and 120 parts by weight of ethyl alcohol. A second solu- 'tion (13) was prepared by adding 2 parts by weightof sodium nitrite to a solution of 2.5 parts by weight of aniline in dilute sulphuric acid (containing 8.5 parts by weight of 93 per cent sulphuric acid and 200 parts by weight of water), followed by the addition of 11.25 parts by weight of sodium acetate. While both (A) and (B) were held at 0 to +5 0., the former wasadded slowly to the latter. A deep red nitro-hydrazone material separated which was recovered by ether extraction, followed by evaporation of the ether. Example 7.-An emulsion was prepared by adding dropwise 2 parts by weight of nitro-hydrazones (from Example 2) dissolved in 3 parts by weight of ethyl alcohol, to a heated (70-80 C.) solution of 1 part by weight of ammonium oleate in 99 parts by weight of water, followed by cooling to room temperature. Example 8.--Two climbing vines (English ivy) were sprayed with the nitro-hydrazone emulsion from Example 7. Each of the two plants was sprayed thoroughly seven times at regular intervals during a period of 28 days. Spraying consisted of allowing the atomized emulsion to impinge onto the foliage until all the upper surfaces were thoroughly wetted. No, noticeable harmful efiects were created by the above spraying.

Example 9.Two peony plants were sprayed with the nitro-hydrazone emulsion prepared according to Example 7. Each plant was sprayed thoroughly seven times at regular intervals during a period or 28 days. The method of spraying Example 10.-Black chrysanthemum aphides were reared in the following manner: .Two chrysanthemum bushes (about 2% to 3 feet in height) were inoculated with black chrysanthemum aphides and the two bushes then covered with closely-woven cheesecloth tents stretched over wire frames. The latter of these were fitted over the bushes and held upright by protruding legs which were stuck into the ground. The cloth covers protected the insects in question from the deleterious effects of rain, wind, etc. After a few weeks the aphides had increased in number so rapidly that a single small twig (2-3 inches in length) carried one to two hundred of these insec Example 11.--Red spiders were reared by inoculating a golden glow plant with these insects and covering the plant by the means described in Example 10. This furnished an available means of procuring red spiders for insecticidal spray tests.

Example 12.Emu1sions of the nitrated codimer as obtained in Example 1 were prepared as follows: to 250 parts by weight of a 1:1000 potassium oleate solution were added slowly 2.5 parts by weight of nitrated co-dimer dissolved in 3 parts by weight of ethyl alcohol, the soap solution being heated to 80-90 C. This resulted in a yellow emulsion. Due to the presence of acidic nitrated groups, a more stable emulsion was obtained by adding a small amount of sodium hydroxide until the emulsion produced a slight pink with phenolphthalein. Due to some evaporation (alcohol and water) during the emulsification step, water was added to the emulsion to adjust its weight to 250 parts.

A more dilute emulsion, one of 1:250 strength of nitrated co-dimer in 1:1000 potassium oleate, was prepared by adding 150 parts by weight of 1:1000 potassium oleate solution to 100 parts by weight of the 1:100 emulsion of nitrated codimer prepared above. A blank solution was prepared, in order to detect any possible efiect of the small amount of alcohol present. This was prepared by adding 3 parts by weight of ethyl alcohol to 250 parts by weight of 1:1000 potassium oleate solution and heating and stirring in the manner described above.

Example 13.-The emulsions of Example 12 were used in spraying aphides reared according to Example and red spiders reared according to Example 11. The tests were run as follows: Twigs were cut from the insect-infested plants of Example 9, and placed on a table consisting of a wooden fra ework with a closely woven cheesecloth top. ach twig was then sprayed from a height of 15 inches with 10 bulbs" of air-emulsion mixture (Example 12), using a hand atomizer in a horizontal position with nozzle tip directed downward onto the twig. By "bulb" is meant the amount of air or insecticide carried by one squeeze of the hand bulb. The

averages of many tests showed that a single squeeze of the bulb carried 47.8 cc. of spray vapor which consisted of 0.2 cc. ofliquid insecticide' solution in an atomized condition, the remainder or 47.6 cc. being air. The sprayed twigs were then covered with halves of 100 mm. diam eter 'Petri dishes and allowedto stand for 24 hours, after which time the twigs were inspected and the insects individually examined and counted by means of tweezers and magnifying glass and classified as alive, dead or moribund. 7

Those insects moribund, ior the sake of calculations, were considered as 50 per cent dead; In other words, for each two that were moribund, one was added to'the list of dead. The results of 1 tests (as used in Example 13), employing black aphides and red spiders reared according to Examples and 11, respectively; The results are tabulated below: For blank runs see Example-13.

vania oil or Example 3 in" 1:1000 potassium oleate solution were prepared by the emulslflcaY- tion procedure of Example 12. .These light-coiored emulsions wereproduced in concentrations of 1:100 and.1:350. They were used in' spray using "potassium oleate solution -.-ot 1:1000

. N be Aiter24hours I111! 1' 1$? mm: Spray Gone. insects ti 2 13:?

. o Dead Alive bum 1. Black chrysantlre- 111mm Pennsylvania 611, 1:250 150 10 72 14 40.5

mnnr aphides. Example '3. '2 in do 1:100 99 54 32 13 61.0 3 Redspiders m 1:250 40 21 1a 0 05.3 4 do -do 1:100 54 43 11 0 79.6

the spray tests using the emulsions of Example Example 16.Emulsions were made using 12 are as follows; nitro-hydrazones from Pennsylvania 011 as ob- I 1 N be Amrmnours I um r 20 Insect Spray Cone. M :5 :5

1 D6811 AHVQ 1 Black ehrysenthemum aphides Water 143 9 134 6.3 2 an do 11:4 1 111 as a an K-ole'ate 111000 12; 18 105 14.0 4 do do 1:101] 80 10 79 10.6 5 -do Ni tgated cedimer Example 1:250 138 81 17 40 73.3 a 'm- 1:250 125 20 01 a1 3010 1 ..mm 1:100 so 00 21 8 no a n n 1:100 82 01 '0 15 83.6 '30 9 Redspiders Water 21 1' 20 4.75 10 n K-ole 1:1000 54 a 40 2 7.4 11 r- Nigated co-dimer Example 1:250 10 13 2 1 s14 12 .110 1 1:100 10 10 100.0

,, Those insects which showed slight leg movement only when said legs were touched with tweezers were considered moribund.

- Example 14.Emu1sions v0i! 1:100 and 12250 tained in Example 4. These emulsions, of 1:100 concentration in 1:1000 potassium oleate soluand 1:250 strengths in 1:1000 potassium oleate time! the nitro-hydrazones as described in Exsolution, were prepared according to the method 40 ample 2, were prepared according to the method of Example 12. These were sprayed (according of Example 12. The emulsions thus obtained to Example 13) onto insects reared as described were stable and of a brownish color. These in Examples 10 and 11, respectively. The results. emulsions were used in spray tests (as in Exare tabulated below. For blank runs see ample 13) employing black aphides (Example Example 13.

4o N W 'Aiter24hours;

, um 13:? Insect Bpny ConclnBw d 2 111 211 Dead Alive a 1 111m chi- 131111161000: Nitrohydruenesfromlenn- 1:210 225 00 115 14 45.1;

aphides. aylv'ania 011, Example 4. y .do.. w 1:100 102 04 1 11 88.0 3 1100;111:101: new 05 a0 a1 2' 09.0 4 do n.- 1:111) 66 50 8 8 81.8 10) and red spiders (Example 11). The results Ezmnple 17.-The nitrated ColombianDiesel follow: For blank runs see Example 13. oil as prepared in Example 5 was converted into v N be. Aitermhours.

' um r 33 Insect Spray Cone. 11$ Mo. K a

4 M QM bnnd 1 Black ohrysanthe- Nitroliydromnesoieo-dimer 1:210 as 21 as s 00.0 mum ephi (Examp .3)-

5 .2 do do 1:250 138 20 113 5 16.3 4 a an do 1:100. 110 me, 1 is 04.5 1 1:... :2 v 1:2: 1: 1: a a s: 3132:3211? 12100 1: 10 1:010 Example 15.-Emulsions' oi nitrated Pennsylemulsions or 1:100 and 1:250 concentrations.

strength. The method of emulsiflcationwas that described in Example 12. These were sprayed, according to Example 13, onto insects reared by the methods of Examples 10 and 11, respectively.

The results follow. For blank runs see Example 13.

rials; these insecticidal materials being applied either in aqueous-soap emulsions or in solution in N be Ai'terflhours um r Insect Spray Cone. insects 11 Dead Alive fi t 1 Black chr santhe- Nitrated Colombian oil oi 1:250 170 87 c 98 40 83.6

mm up des. Example 6.

2 dn rln him 125 45 10 60.0 3 Red sp do 1:260 23 10 6 8 .6118 4 "do -do 1:100 36 22 6 7 73.0

Example 18.The nitro-hydrazones obtained from Colombian oil as in Examplefi were converted into emulsions of 1:100 and 1:250 concentrations. Aqueous potassium oleate 1:1000 was used as the dispersing medium and the emulsions were prepared following the method as outlined in Example 12. Spray tests were made accordin to Example 13, using aphides (Example 10) and red spiders (Example 11) The tabulated results are shown below. For blank runs see Example organic solvents, or in colloidal clay suspensions, and the'like.

What I claim is:

1. A. horticultural contact insecticide consisting of nitrated oleflns, said olefins derived from petroleum.

2. A contact hydraz'ones.

3. A contact insecticide which comprises nitrohydrazones, said nitro-hydrazones being derived insecticide which comprises nitro- 13. from nitrated petroleum dlstillates.

N be! AiterMhours Insect Spray Conc, insects m Dead Alive bund' 1 Black chrysanthe- Nitroh drazonee from Comoo 10s 15s 10 10.2 mum aphides. lomb an oil (Example 6).

2 d0 d0 moo m as 12 on a Red spiders do 1:250 so e1 25 4 10.0

4 dn in 1:100 52 as 12 s 72.0

It will be seen from the foregoing that my invention comprises treating hydrocarbon starting materials ggoleflnic, saturated parafllnic, naphthenic, or aryl or aralkyl in nature), derivable from petroleum, with a nitrating agent and separating the nitrated products and refining same, for example, by water-washing and drying. My invention further comprises the condensation of said nitrated hydrocarbons with diazonium compounds, and separating and refining the nitrohydrazones thus obtained. My invention comprises further the use of said nitrated hydrocar bons and nitro-hydrazones as insecticidal mate- 4. A contact insecticide which comprises nitrohydrazones, said nitro-hydrazones being derived from,nitrated oleflns.

5. A contact insecticide which comprises nitrohydrazones, said nitro-hydramnes being formed by the condensation of nitrated petroleum distillates with phenyldiazonium chloride. 1

6. A contact insecticide which comprises nitrohydrazones, said nitro-hydrazones being formed by the condensation of nit-rated olefins with phenyldiazonium chloride.

CARIETDN was. 

